A guide to supramolecular polymerizations

Hartlieb, Matthias; Mansfield, Edward D. H.; Perrier, Sébastien

doi:10.1039/c9py01342c

Cited by 112 publications

(98 citation statements)

References 241 publications

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“… 5 , 10 They are also ideal candidates for the formation of supramolecular gels, 11 − 13 which hold great potential on the basis of their intricate properties, 14 − 17 such as chiral selection, 18 amplification, 19 and microactuation. 20 , 21 Elegant mathematical models have been developed for different types of polymerization mechanisms, 1 − 4 e.g. isodesmic, 22 cooperative, 23 , 24 and others, 25 , 26 revealing the dynamic and tunable nature of synthetic supramolecular systems and providing the tools for controlling their assembly processes.…”

Section: Introductionmentioning

confidence: 99%

From Photoinduced Supramolecular Polymerization to Responsive Organogels

Pfeifer

Crespi

et al. 2021

J. Am. Chem. Soc.

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Controlling supramolecular polymerization by external stimuli holds great potential toward the development of responsive soft materials and manipulating self-assembly at the nanoscale. Photochemical switching offers the prospect of regulating the structure and properties of systems in a noninvasive and reversible manner with spatial and temporal control. In addition, this approach will enhance our understanding of supramolecular polymerization mechanisms; however, the control of molecular assembly by light remains challenging. Here we present photoresponsive stiff-stilbene-based bis-urea monomers whose trans isomers readily form supramolecular polymers in a wide range of organic solvents, enabling fast light-triggered depolymerization–polymerization and reversible gel formation. Due to the stability of the cis isomers and the high photostationary states (PSS) of the cis – trans isomerization, precise control over supramolecular polymerization and in situ gelation could be achieved with short response times. A detailed study on the temperature-dependent and photoinduced supramolecular polymerization in organic solvents revealed a kinetically controlled nucleation–elongation mechanism. By application of a Volta phase plate to enhance the phase-contrast method in cryo-EM, unprecedented for nonaqueous solutions, uniform nanofibers were observed in organic solvents.

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Section: Introductionmentioning

confidence: 99%

From Photoinduced Supramolecular Polymerization to Responsive Organogels

Pfeifer

Crespi

et al. 2021

J. Am. Chem. Soc.

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“…A large kinetic barrier to prevent spontaneous nucleation (also called “spurious nucleation”) of monomers must be in place, while added seeds must readily bypass that barrier to yield rapid growth. Barriers can be constructed by kinetic trapping of monomers into inactive states (see Supplementary Discussion 1 for more discussion), and/or by making stable capture of incoming monomers contingent on the cooperative binding of two or more previously acquired neighbors (i.e., half the monomer coordination number) 1 – 38 . In the latter case—which we refer to here as joint-neighbor capture of monomers—a large coordination number would allow two prized characteristics of self-assembly that otherwise would be mutually exclusive for such systems: near-complete suppression of spontaneous nucleation 39 , 40 along with rapid, irreversible growth from introduced seeds.…”

Section: Introductionmentioning

confidence: 99%

Robust nucleation control via crisscross polymerization of highly coordinated DNA slats

et al. 2021

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Natural biomolecular assemblies such as actin filaments or microtubules can exhibit all-or-nothing polymerization in a kinetically controlled fashion. The kinetic barrier to spontaneous nucleation arises in part from positive cooperativity deriving from joint-neighbor capture, where stable capture of incoming monomers requires straddling multiple subunits on a filament end. For programmable DNA self-assembly, it is likewise desirable to suppress spontaneous nucleation to enable powerful capabilities such as all-or-nothing assembly of nanostructures larger than a single DNA origami, ultrasensitive detection, and more robust algorithmic assembly. However, existing DNA assemblies use monomers with low coordination numbers that present an effective kinetic barrier only for slow, near-reversible growth conditions. Here we introduce crisscross polymerization of elongated slat monomers that engage beyond nearest neighbors which sustains the kinetic barrier under conditions that promote fast, irreversible growth. By implementing crisscross slats as single-stranded DNA, we attain strictly seed-initiated nucleation of crisscross ribbons with distinct widths and twists.

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“…AFM can be used to image the molecular structure of the assemblies in solution even though the drying process can inevitably cause some changes. 30 To this end, dilute solutions of 1 in CH 3 Cl were spin-coated onto mica surfaces, and AFM studies were accomplished in tapping mode. The studies revealed the presence of spherical-shaped structures with a hollow core (donut-like structures) of different sizes ( Figure 3 ), suggesting the formation of oligomers with variable length.…”

Section: Resultsmentioning

confidence: 99%

Self-Assembly-Directed Organization of a Fullerene–Bisporphyrin into Supramolecular Giant Donut Structures for Excited-State Charge Stabilization

et al. 2021

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Functional materials composed of spontaneously self-assembled electron donor and acceptor entities capable of generating long-lived charge-separated states upon photoillumination are in great demand as they are key in building the next generation of light energy harvesting devices. However, creating such well-defined architectures is challenging due to the intricate molecular design, multistep synthesis, and issues associated in demonstrating long-lived electron transfer. In this study, we have accomplished these tasks and report the synthesis of a new fullerene–bis-Zn-porphyrin e -bisadduct by tether-directed functionalization of C 60 via a multistep synthetic protocol. Supramolecular oligomers were subsequently formed involving the two porphyrin-bearing arms embracing a fullerene cage of the vicinal molecule as confirmed by MALDI-TOF spectrometry and variable temperature NMR. In addition, the initially formed worm-like oligomers are shown to evolve to generate donut-like aggregates by AFM monitoring that was also supported by theoretical calculations. The final supramolecular donuts revealed an inner cavity size estimated as 23 nm, close to that observed in photosynthetic antenna systems. Upon systematic spectral, computational, and electrochemical studies, an energy level diagram was established to visualize the thermodynamic feasibility of electron transfer in these donor–acceptor constructs. Subsequently, transient pump–probe spectral studies covering the wide femtosecond-to-millisecond time scale were performed to confirm the formation of long-lived charge-separated states. The lifetime of the final charge-separated state was about 40 μs, thus highlighting the significance of the current approach of building giant self-organized donor–acceptor assemblies for light energy harvesting applications.

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A guide to supramolecular polymerizations

Abstract: Supramolecular polymers are non-covalent assemblies of unimeric building blocks connected by secondary interactions and hold great promises due to their dynamic nature.

Cited by 112 publications

References 241 publications

From Photoinduced Supramolecular Polymerization to Responsive Organogels

From Photoinduced Supramolecular Polymerization to Responsive Organogels

Robust nucleation control via crisscross polymerization of highly coordinated DNA slats

Self-Assembly-Directed Organization of a Fullerene–Bisporphyrin into Supramolecular Giant Donut Structures for Excited-State Charge Stabilization

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